US20250023048A1 - Acrylate binder - Google Patents

Acrylate binder Download PDF

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US20250023048A1
US20250023048A1 US18/712,625 US202218712625A US2025023048A1 US 20250023048 A1 US20250023048 A1 US 20250023048A1 US 202218712625 A US202218712625 A US 202218712625A US 2025023048 A1 US2025023048 A1 US 2025023048A1
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monomer
polymer
group
electrode
composition
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Jean Noël Tourvieille
Steven Meeker
Stefano Mauri
Maurizio Biso
Wojciech Bzducha
Jean-Christophe Castaing
David James Wilson
Jean Raoul Gomez
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Syensqo Specialty Polymers Italy SpA
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Solvay Specialty Polymers Italy SpA
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Assigned to SOLVAY SPECIALTY POLYMERS ITALY S.P.A. reassignment SOLVAY SPECIALTY POLYMERS ITALY S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GOMEZ, Jean Raoul, BZDUCHA, WOJCIECH, CASTAING, JEAN-CHRISTOPHE, WILSON, DAVID JAMES, BISO, MAURIZIO, MAURI, STEFANO, MEEKER, Steven, TOURVIEILLE, Jean Noël
Publication of US20250023048A1 publication Critical patent/US20250023048A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a polymer for use in non-aqueous electrolyte rechargeable battery, an electrode slurry for a rechargeable battery and a rechargeable battery comprising the same.
  • Silicon (Si) has been extensively studied as anode active material due to its high theoretical specific capacity (3600 mAh/g), much higher than the incumbent anode active material, graphite ( ⁇ 400 mAh/g).
  • Si is highly challenging because during lithium insertion and extraction (charge and discharge of the battery) a dramatic volume change hasten mechanical fracture of the electrode causing loss of electric contact and resulting in continuous electrolyte decomposition at the active material surface.
  • One widely adopted strategy in the battery market is to use a limited amount of silicon ( ⁇ 10%) mixed with graphite as active material. This strategy mitigates the detrimental impact of silicon on electrode mechanical integrity; however, the achieved improvement in energy density, proportional to the amount of silicon, is quite limited.
  • the binder typically an organic polymer, serves as the connective matrix that maintains contact between active materials throughout the anode layer and with the current collector onto which the anode is deposited during fabrication.
  • the binder currently used at anode is a combination of a rubber (SBR) with a cellulose derivative (CMC).
  • SBR rubber
  • CMC cellulose derivative
  • Said binder is not adequate for silicon-rich anodes (silicon amount >10%) because it is not sufficiently rigid. More efforts to achieve Si-rich anodes (>10%) are still needed especially on binder design, because the binder can play a key role in accommodating volume change and prevent electrical contact loss between Si particles.
  • a robust polymeric binder capable to interact reversibly with the surface of silicon, can inhibit mechanical fracturing of the anodes during cycling.
  • polycarboxylate binders and derivatives are being pursued, including polyacrylic acids, polyamic acids, polyacrylamides, and other hydrogen bonding structures.
  • WO 2022/013070 discloses that certain modified polycarboxylates polymers, especially modified polyacrylic acids including acrylamide monomers, allow preventing degradation of silicon-rich anodes.
  • the distribution of the acrylic acid (AA) and acrylamide (AM) monomers in said polymers grants excellent adhesion to metal in comparison with lithiated polyacrylic acid (PAA).
  • PAA lithiated polyacrylic acid
  • the anodes obtained by using said polymers as binders show good cycling stability, which is related to the higher cohesion that the polymers have in comparison with SBR/CMC systems.
  • Such binders types effectively make hydrogen bonding between pendant acid groups and silanol groups on the silicon surface and this addresses the silicon volume change issue but they have no favorable rheology and dispersant behaviors. So they need additives like carboxymethylcellulose (CMC), a well know rheology modifier and dispersant, for effective electrode preparation.
  • CMC carboxymethylcellulose
  • the Applicant has unexpectedly found that certain polycarboxylates polymers, properly lithiated, show surprisingly excellent dispersant properties, and are therefore suitable for anode slurry preparation, even in the absence of dispersants.
  • an acrylic polymer dispersant for dispersing powder particles in aqueous electrode-forming compositions, characterized by comprising:
  • polymer (P) dissolved in water can be suitably used as binder for the preparation of electrode-forming compositions thanks to its excellent dispersing ability, far better than that of CMC or of blends of CMC with acrylic polymers.
  • the polymer (P) in fact leads to stable slurry with no sedimentation for over 2 days without the use of a rheology modifier.
  • composition (Comp) for use in the preparation of electrodes for electrochemical devices, said composition being characterized by consisting of:
  • the present invention provides a process for preparing an electrode [electrode (E)], said process comprising:
  • the present invention pertains to the electrode [electrode (E)] obtainable by the process of the invention.
  • the present invention pertains to an electrochemical device comprising at least one electrode (E) of the present invention.
  • FIG. 1 are optical microscopy images of formulations 1 to 3 of the examples.
  • percent by weight indicates the content of a specific component in a mixture, calculated as the ratio between the weight of the component and the total weight of the mixture.
  • weight percent indicates the ratio between the weight of all non-volatile ingredients in the liquid.
  • electrochemical cell By the term “electrochemical cell”, it is hereby intended to denote an electrochemical cell comprising a positive electrode, a negative electrode and a liquid electrolyte, wherein a monolayer or multilayer separator is adhered to at least one surface of one of said electrodes.
  • Non-limitative examples of electrochemical cells include, notably, batteries, preferably secondary batteries, and electric double layer capacitors.
  • secondary battery it is intended to denote a rechargeable battery.
  • Non-limitative examples of secondary batteries include, notably, alkaline or alkaline-earth secondary batteries.
  • an electrode forming composition is a composition of matter, typically a fluid composition, wherein solid components are dissolved or dispersed in a liquid, which can be applied onto a metallic substrate and subsequently dried thus forming an electrode wherein the metallic substrate acts as current collector.
  • Electrode forming compositions typically comprise at least an electro active material and at least a binder.
  • the electrode-forming composition [composition (Comp)] of the present invention comprises at least one polymer (P), which functions as a binder.
  • Polymer (P) is characterized by comprising recurring units derived from at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer [monomer (AA)] in neutralized form and recurring units derived from at least one (meth)acrylamide monomer [monomer (AM)].
  • the at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer (AA) is preferably a compound of formula (I):
  • monomer (AA) is a compound of formula (I) as above defined, that is selected from the group consisting of salts of: acrylic acid, methacrylic acid, Sipomer® B-CEA (sold by Solvay), ethacrylic acid, crotonic, methyl (meth)acrylic acid, ethyl (meth)acrylic acid, propyl (meth)acrylic acid, isopropyl (meth)acrylic acid, n-butyl (meth)acrylic acid, 2-ethylhexyl (meth)acrylic acid, n-hexyl (meth)acrylic acid and n-octyl (meth)acrylic acid.
  • the (meth)acrylamide monomer [monomer (AM)] is preferably a compound of formula (II):
  • the monomer (AM) is preferably selected from the group consisting of (meth)acrylamides or N-substituted (meth)acrylamide such as N-alkyl acrylamides, N,N-dialkylacrylamides.
  • Polymer (P) may optionally include recurring units derived from at least one ethylenically unsaturated monomer (M), different from monomer (AA) and from monomer (AM), provided the total amount of monomer (AA) and/or monomer (AM) is at least 60% by moles with respect to the total moles of recurring units of polymer (P).
  • M ethylenically unsaturated monomer
  • AM monomer
  • Monomer (M) can suitably be selected from the group consisting of:
  • Polymer (P) can be obtained by radical copolymerization of a mixture of at least one monomer (AA), at least one monomer (AM) and optionally at least one monomer (M) as above defined, to provide a polymer (P—H), followed by neutralization of the acid groups of the recurring units derived from monomer (AA), wherein the neutralization of acid groups is carried out either with a salt [salt (S)] including a monovalent cation, preferably an alkaline metal salt, in a suitable solvent, or with ammonia.
  • a salt [salt (S)] including a monovalent cation, preferably an alkaline metal salt preferably an alkaline metal salt
  • the salt (S) can be any salt capable of neutralizing the acid groups.
  • the salt (S) is a lithium salt selected from the group consisting of lithium carbonate, lithium hydroxide, lithium bicarbonate, and combinations thereof, preferably lithium carbonate.
  • the lithium salt is free of lithium hydroxide.
  • the solvent for use in the step of neutralization of polymer (P—H) can be any solvent capable of dissolving the salt (S) or ammonia and the resulting polymer (P).
  • the solvent is selected from at least one of an aqueous solvent, such as water, NMP, and alcohols, such as, for example, methanol, isopropanol, and ethanol.
  • the solvent is an aqueous solvent. Still more preferably the solvent is water.
  • the content of the salt (S) in the solvent ranges from 0.5 to 10 wt %, preferably from 1 to 5 wt %, based on the total weight of the solvent and the salt (S).
  • the concentration of the lithium salt in the solvent provides at least 0.25 eq, 0.5 eq, 0.8 eq, 1 eq, 1.5 eq, 2 eq, 2.5 eq, 3 eq, 4, eq of lithium to acid groups.
  • the concentration of the lithium salt in the solvent provides at most 5 eq, preferably at most 4, eq of lithium to acid groups.
  • the polymer (P) comprises recurring units derived from the lithiated form of the at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer.
  • the content of polymer (P) in the solution after neutralization ranges from 0.5 to 40 wt %, preferably from 2 to 30 wt %, more preferably 4 to 20 wt %.
  • a lithium salt of polymer (P), namely polymer (P—Li) was prepared by adding an amount of LiOH to at least partially fully neutralize an aqueous solution containing about 10 wt % polymer (P—H).
  • the resulting solution had a pH in the range of 6.5 to 9, preferably in the range of 7 to 8 and contained approximately 10 wt % of polymer (P—Li).
  • the neutralized polymer solution has advantages in the processing and dispersing ability of the slurry because neutralized polymer shows increased viscosity. Moreover, polymer (P—Li) has a pH more compatible with lithiated silicon types that usually show better performance if processed with slurry having a pH higher than 7.
  • the linkage A and the residue R 2 may be attached to the heterocyclic group at any position, either on carbon or nitrogen atom.
  • the monomer (M1) may for example be:
  • the divalent spacer group A in formula (III) may typically be group —CO—NH—(CH 2 ) n —, —CO—O—(CH 2 ) n or —CO—O—(CH 2 ) n —O—CO—, but any other covalent linker group may be contemplated, for example resulting from the reaction of a compound of formula (III-X):
  • the polymer (P) is a polymer as obtained by copolymerizing monomers (AA), (AM) and at least one monomer (M1) to obtain polymer (P—H), namely having the structure that is obtained via such a polymerization, followed by neutralization of the acid groups of the recurring units derived from monomer (AA); but the polymer (P) is not necessarily obtained by this process.
  • the compound (III-X) used in the step (E1) may advantageously be selected from: additional acrylic or methacrylic acid, or ester thereof; maleic anhydride; vinylbenzyl chloride; glycidylmethacrylate; and (blocked) isocyanatoethyl methacrylate.
  • the compound (III-X) used in the step (E1) may advantageously be selected from additional acrylic acid, methacrylic acid, maleic anhydride or their esters.
  • a quaternization of all or part of the imidazole functions of polymer may occur, resulting from a quaternization of all or part of the monomers and/or form a post-quaternization of all or part of the imidazole functions of the polymer.
  • polymer (P) comprises at least one monomer (M2) of formula (IV) as above defined.
  • the “heterocyclic group” in residue R x of monomer (M2) includes saturated heterocyclic group having at least one nitrogen atom compound, such as imidazolidinone.
  • the monomer (M2) may for example be a compound of formula (IVa)
  • the monomer (M2) may for example be a compound of formula (IVd)
  • the polymer (P) is a polymer as obtained by copolymerizing monomers (AA), (AM) and at least one monomer (M2), to obtain polymer (P—H), namely having the structure that is obtained via such a polymerization, followed by neutralization of the acid groups of the recurring units derived from monomer (AA); but the polymer (P—H) is not necessarily obtained by this process.
  • polymer (P) may comprise one or more further monomers (M3) as above defined.
  • the proportion in moles of monomers (M3) in polymer (P) is below 5% by moles.
  • the at least one polymer (P) may further comprise below 1% by moles of one or more further crosslinking monomers (XL-M) comprising at least two ethylenic unsaturations.
  • said crosslinking monomers may be chosen from N,N′-methylenebisacrylamide (MBA), N,N′-ethylenebisacrylamide, polyethylene glycol (PEG) diacrylate, triacrylate, divinyl ether, typically trifunctional divinyl ether, for example tri(ethylene glycol) divinyl ether (TEGDE), N-diallylamines, N,N-diallyl-N-alkylamines, the acid addition salts thereof and the quaternization products thereof, the alkyl used here being preferentially (C 1 -C 3 )-alkyl; compounds of N,N-diallyl-N-methylamine and of N,N-diallyl-N,N-dimethylammonium, for example the chlorides and bromides; or alternatively ethoxylated trimethylolpropane triacylate, ditrimethylolpropane tetraacrylate (DiTMPTTA), diviny
  • the proportion in moles of monomers (XL-M) cannot exceed 1% by moles of the total moles of monomers present in polymer (P) to avoid gel formation and viscosity increase.
  • the proportion in moles of monomers (XL-M) is below 0.5% by moles.
  • polymer (P) there are no monomers (M3) or (XL-M) in the polymer (P), which means that polymer (P—H) is obtained by radical copolymerization of a mixture consisting essentially of, notably consisting of:
  • the polymer (P) is obtained by radical copolymerization of a mixture of:
  • Any source of free radicals can be used. It is possible in particular to generate free radicals spontaneously, for example by increasing the temperature, with appropriate monomers, such as styrene. It is possible to generate free radicals by irradiation, in particular by UV irradiation, preferably in the presence of appropriate UV-sensitive initiators. It is possible to use initiators or initiator systems of radical or redox type.
  • the source of free radicals may or may not be water-soluble. It may be preferable to use water-soluble initiators or at least partially water-soluble initiators.
  • Use may in particular be made of the following initiators:
  • the polymerization temperature can in particular be between 25° C. and 95° C.
  • the temperature can depend on the source of free radicals. If it is not a source of UV initiator type, it will be preferable to operate between 50° C. and 95° C., more preferably between 60° C. and 80° C. Generally, the higher the temperature, the more easily the polymerization is initiated (it is promoted) but the lower the molar masses of the copolymers obtained.
  • Polymer (P—H) can also be prepared by any controlled radical polymerization technique. Among these, reversible addition-fragmentation chain transfer (RAFT) and macromolecular design via inter-exchange of xanthate (MADIX) can be mentioned.
  • RAFT reversible addition-fragmentation chain transfer
  • MADIX macromolecular design via inter-exchange of xanthate
  • RAFT/MADIX agents RAFT or MADIX controlled radical polymerization agents, hereinafter referred to as “RAFT/MADIX agents”, has been disclosed for instance WO 98/058974 A (RHODIA CHIMIE) 30 Dec. 1998 and WO 98/01478 A (E.I. DUPONT DE NEMOURS AND COMMONWEALTH SCIENTIFIC AND INDUSTRIAL RESEARCH ORGANIZATION) 15 Jan. 1998.
  • the polymer (P—H) is obtained by radical copolymerization of a mixture having the following molar ratio, based on the total quantity of monomer (AA), monomer (AM) and monomer (M):
  • polymer (P) preferably comprises:
  • the polymer (P) according to the invention has a weight average molecular weight of about 500 kDa to 10000 kDa.
  • polymer (P) is a statistical (random) copolymer having a weight average molecular weight of about 500 kDa to 10000 kDa, which is obtained by radical polymerization of a mixture of monomer (AA), monomer (AM), and a monomer (M), preferably in a molar ratio of about:
  • polymer (P) is a block copolymer obtained by controlled radical polymerization using RAFT/MADIX agents.
  • block copolymer as used herein it is intended any controlled-architecture copolymer, including but not limited to true block polymers, which could be di-blocks, tri-blocks, or multi-blocks; branched block copolymers, also known as linear star polymers; comb; and gradient polymers.
  • Gradient polymers are linear polymers whose composition changes gradually along the polymer chains, potentially ranging from a random to a block-like structure.
  • Each block of the block copolymers may itself be a homopolymer, a random copolymer, a random terpolymer, or a gradient polymer.
  • polymer (P) is obtained by radical polymerization of an acrylic acid, an acrylamide and vinylimidazole of formula (IIIa), followed by neutralization of the acid groups of the recurring units derived from monomer (AA), preferably with LiOH.
  • the Electrode-Forming Composition [Composition (Comp)]
  • the electrode forming composition [composition (Comp)] of the present invention includes one or more electrode active material.
  • electrode active material is intended to denote a compound that is able to incorporate or insert into its structure, and substantially release therefrom, alkaline or alkaline-earth metal ions during the charging phase and the discharging phase of an electrochemical device.
  • the electrode active material is preferably able to incorporate or insert and release lithium ions.
  • the electrode active material may comprise a composite metal chalcogenide of formula LiMQ 2 , wherein M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V and Q is a chalcogen such as O or S.
  • M is at least one metal selected from transition metals such as Co, Ni, Fe, Mn, Cr and V
  • Q is a chalcogen such as O or S.
  • Preferred examples thereof may include LiCoO 2 , LiNiO 2 , LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 1) and spinel-structured LiMn 2 O 4 .
  • the electrode active material may comprise a lithiated or partially lithiated transition metal oxyanion-based electro-active material of formula M 1 M 2 (JO 4 ) f E 1-f , wherein M 1 is lithium, which may be partially substituted by another alkali metal representing less than 20% of the M 1 metals, M 2 is a transition metal at the oxidation level of +2 selected from Fe, Mn, Ni or mixtures thereof, which may be partially substituted by one or more additional metals at oxidation levels between +1 and +5 and representing less than 35% of the M2 metals, including 0, JO 4 is any oxyanion wherein J is either P, S, V, Si, Nb, Mo or a combination thereof, E is a fluoride, hydroxide or chloride anion, f is the molar fraction of the JO 4 oxyanion, generally comprised between 0.75 and 1.
  • the M 1 M 2 (JO 4 ) f E 1-f electro-active material as defined above is preferably phosphate-based and may have an ordered or modified olivine structure.
  • the electrode active material in the case of forming a positive electrode has formula Li 3-x M′ y M′′ 2-y (JO 4 ) 3 wherein 0 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 2, M′ and M′′ are the same or different metals, at least one of which being a transition metal, JO 4 is preferably PO 4 which may be partially substituted with another oxyanion, wherein J is either S, V, Si, Nb, Mo or a combination thereof. Still more preferably, the electrode active material is a phosphate-based electro-active material of formula Li(Fe x Mn 1-x )PO 4 wherein 0 ⁇ x ⁇ 1, wherein x is preferably 1 (that is to say, lithium iron phosphate of formula LiFePO 4 ).
  • the electrode active material may preferably comprise one or more carbon-based materials and/or one or more silicon-based materials.
  • the carbon-based materials may be selected from graphite, such as natural or artificial graphite, graphene, or carbon black. These materials may be used alone or as a mixture of two or more thereof.
  • the carbon-based material is preferably graphite.
  • the silicon-based compound may be one or more selected from the group consisting of chlorosilane, alkoxysilane, aminosilane, fluoroalkylsilane, silicon, silicon chloride, silicon carbide, silicon oxide and lithiated silicon.
  • the silicon-based compound may be silicon oxide or silicon carbide.
  • the silicon-based compounds are comprised in an amount ranging from 1 to 70% by weight, preferably from 5 to 30% by weight with respect to the total weight of the electro active compounds.
  • One or more optional electroconductivity-imparting additives may be added in order to improve the conductivity of a resulting electrode made from the composition of the present invention.
  • Conducting agents for batteries are known in the art.
  • Examples thereof may include: carbonaceous materials, such as carbon black, graphite fine powder, carbon nanotubes, graphene, or fiber, or fine powder or fibers of metals such as nickel or aluminum.
  • the optional conductive agent is preferably carbon black. Carbon black is available, for example, under the brand names, Super P® or Ketjenblack®.
  • the conductive agent is different from the carbon-based material described above.
  • the optional conductive agent is typically from 0 wt. % to 5 wt. %, more preferably from 0 wt. % to 2 wt. % of the total amount of the solids within the composition, while for anode forming compositions comprising silicon based electro active compounds it has been found to be beneficial to introduce a larger amount of optional conductive agent, typically from 0.5 to 30 wt. % of the total amount of the solids within the composition.
  • polymer (P) The surprising excellent dispersing ability shown by polymer (P), despite the very high molecular weight, makes polymer (P) suitable for use as binder in the preparation of electrode-forming compositions having an excellent rheological profile, thus to stable slurry with no sedimentation for over 2 days without the use of a rheology modifier.
  • composition (Comp) does not include any rheology modifier such as CMC, and thanks to the excellent dispersing ability of polymer (P), the amount of polymer (P) in the electrode-forming composition can be raised.
  • the amount of polymer (P) in composition (Comp) is suitably of about 2 to 10%, preferably of about 3 to 5% of the total amount of the solids within the composition.
  • polymer (P) allows to obtain compositions with higher binder content, with advantages in terms of higher efficiency, higher productivity and higher battery energy obtained.
  • composition (Comp)] of the present invention thanks to the excellent dispersing ability of polymer (P), allows to obtain compositions with augmented total solid content (TSC), which is not trivial in the absence of rheology modifiers such as CMC.
  • the total solid content (TSC) of the composition (Comp) of the present invention is typically higher than 40%, preferably from 40 to 70 wt. % over the total weight of the composition (Comp).
  • the total solid content of the composition (Comp) is understood to be cumulative of all non-volatile ingredients thereof, notably including polymer (P), the electrode active material and any solid, non-volatile additional additive.
  • composition (Comp) may be prepared according to any method known to the skilled person.
  • the electrode forming composition (Comp) of the present invention can be prepared by a process comprising the following steps:
  • composition (Comp) When the aqueous solution of polymer (P) is prepared separately and subsequently combined with an electrode active material and optional conductive material and other additives to prepare composition (Comp), an amount of water sufficient to create a stable solution is employed.
  • the amount of water used may range from the minimum amount needed to create a stable solution to an amount needed to achieve a desired total solid content in an electrode mixture after the active electrode material, optional conductive material, and other solid additives have been added.
  • the electrode-forming composition (Comp) of the invention can be used in a process for the manufacture of an electrode [electrode (E)], said process comprising:
  • the metal substrate is generally a foil, mesh or net made from a metal, such as copper, aluminum, iron, stainless steel, nickel, titanium or silver.
  • the electrode forming composition (Comp) is applied onto at least one surface of the metal substrate typically by any suitable procedures such as casting, printing and roll coating.
  • step (iii) may be repeated, typically one or more times, by applying the electrode forming composition (Comp) provided in step (ii) onto the assembly provided in step (iv).
  • the drying temperature will be selected so as to effect removal by evaporation of the aqueous medium from the electrode (E) of the invention.
  • step (v) the dried assembly obtained in step (iv) is submitted to a compression step such as a calendaring process, to achieve the target porosity and density of the electrode (E) of the invention.
  • the dried assembly obtained at step (iv) is hot pressed, the temperature during the compression step being comprised from 25° C. and 130° C., preferably being of about 60° C.
  • Preferred target density for electrode (E) is comprised between 1.4 and 2 g/cc, preferably at least 1.55 g/cc.
  • the density of electrode (E) is calculated as the sum of the product of the densities of the components of the electrode multiplied by their mass ratio in the electrode formulation.
  • the present invention pertains to the electrode [electrode (E)] obtainable by the process of the invention.
  • an electrode (E) comprising:
  • the composition directly adhered onto at least one surface of said metal substrate corresponds to the electrode forming composition (Comp) of the invention wherein the aqueous solvent has been at least partially removed during the manufacturing process of the electrode, for example in step (iv) (drying) and/or in the compression step (v). Therefore all the preferred embodiments described in relation to the electrode forming compositions (Comp) of the invention are also applicable to the composition directly adhered onto at least one surface of said metal substrate, in electrodes of the invention, except for the aqueous medium removed during the manufacturing process.
  • the present invention relates to a negative electrode comprising, based on the total weight of the electrode:
  • the Applicant has surprisingly found that the electrode according to the present invention is endowed with good mechanical properties and impressive cycle stability.
  • the binder comprising the polymer (P) of the present invention shows higher adhesion to current collector compared to SBR/CMC binders, but also to binders comprising polymer (P) and a rheology modifier such as CMC and to salified PAA.
  • the secondary battery of the invention is preferably an alkaline or an alkaline-earth secondary battery.
  • the secondary battery of the invention is more preferably a lithium-ion secondary battery.
  • An electrochemical device according to the present invention can be prepared by standard methods known to a person skilled in the art.
  • the synthesis process was conducted in a thermally isolated reactor to minimize the heat exchange with surrounding (Thermos like flask).
  • the reactor was equipped with a lid containing multiple entries into which were installed a small reflux system, a mechanical stirring system, a nitrogen purge line and a raw materials feed line.
  • all monomers, solvent (water) and a transfer agent were charged into the reactor and kept under stirring and nitrogen purging for around 1 hour at room temperature.
  • the redox type initiator was added to the reaction mixture.
  • the thermal initiator was also added at same time into the reaction mixture. The initiator was homogenized in the reaction mixture for few minutes with mechanical stirring, then the stirring and nitrogen purge were stopped.
  • reaction mixture temperature from room temperature up to around 80-90° C. was obtained within around half to one hour time as an exothermic effect. Then, the reaction mixture was maintained in the reaction flask for further 24 hours. Aqueous solution of polymer (P) were thus obtained.
  • Polymer (P-1H), (P-2H) and (P-3H) aqueous solutions obtained as above described were titrated with a LiOH aqueous solution (4.25% by weight of LiOH in water) using a titrator T5 from Mettler Toledo until pH 7.5. Solutions with final lithiated P-1, P-2 and P-3 polymers concentration in water of 7.5 or 5 wt. % were prepared.
  • Evaluation of the dispersing ability of polymer P-1 was made using an aqueous formulation comprising CB and the polymer P-1, in comparison with aqueous formulations having the same viscosity and comprising CB alone, CB with CMC, and CB with CMC and polymer P-1.
  • the aqueous formulations were submitted to orbitary mixing (Thinky ARE 250) for a sequence of 2000 rpm for 10 min.
  • the dispersion state of the carbon black was assessed by optical microscopy. The results are described in the Table 3 below.
  • microscopy images of formulations 1 to 3 are reported in FIG. 1 .
  • the low-shear viscosity taken at a shear rate of 0.1 s-1 is given in Table 4.
  • the use of the polymer dispersant according to the present invention allows using formulations with higher amounts of binder without affecting the rheology of the binder itself.
  • Example 1 Tepolymer Anode 5% Binder
  • a negative electrode was obtained by casting the composition thus obtained on a 10 ⁇ m thick copper foil with a doctor blade and drying the coating layer in an oven at temperature of 90° C. for about 70 minutes. The thickness of the dried coating layer was about 72 ⁇ m. The electrode was then hot pressed at 60° C. in a roll press to achieve target density of 1.6 g/cc.
  • the resulting negative electrode had the following composition: 18.8 wt. % of silicon oxide, 75.2 wt. % of graphite, 5 wt. % of P-1 and 1 wt. % of carbon black. Electrode E1 was thus obtained.
  • a negative electrode was obtained by casting the composition thus obtained on a 10 ⁇ m thick copper foil with a doctor blade and drying the coating layer in an oven at temperature of 90° C. for about 70 minutes. The thickness of the dried coating layer was about 68 ⁇ m. The electrode was then hot pressed at 60° C. in a roll press to achieve target density of 1.6 g/cc.
  • the resulting negative electrode had the following composition: 19.2 wt. % of silicon oxide, 76.8 wt. % of graphite, 3 wt. % of P-1 and 1 wt. % of carbon black. Electrode E3 was thus obtained.
  • a negative electrode was obtained by casting the composition thus obtained on a 10 ⁇ m thick copper foil with a doctor blade and drying the coating layer in an oven at temperature of 90° C. for about 70 minutes. The thickness of the dried coating layer was about 69 ⁇ m. The electrode was then hot pressed at 60° C. in a roll press to achieve target density of 1.6 g/cc.
  • the resulting negative electrode had the following composition: 19.2 wt. % of silicon oxide, 76.8 wt. % of graphite, 2 wt. % of SBR, 1 wt. % of CMC and 1 wt. % of carbon black. Electrode CE1 was thus obtained
  • An aqueous composition was prepared by mixing 19.0 g of a 2% by weight solution of CMC, in water, 0.38 g of carbon black, 7.14 g of silicon oxide, 28.58 g of graphite and 24.6 g of deionized water. After moderate stirring in the planetary mixer for 10 min, 20.27 g of a 7.5% solid content solution in water of polymer P-1 was added. The mixture was homogenized by moderate stirring in a planetary mixer for 10 min and then mixed again by moderate stirring for 1 h. After 1 h, the shear was reduced and the slurry mixed again by low stirring.
  • a negative electrode was obtained by casting the composition thus obtained on a 10 ⁇ m thick copper foil with a doctor blade and drying the coating layer in an oven at temperature of 90° C. for about 70 minutes. The thickness of the dried coating layer was about 74 ⁇ m. The electrode was then hot pressed at 60° C. in a roll press to achieve target density of 1.6 g/cc.
  • the resulting negative electrode had the following composition: 18.8 wt. % of silicon oxide, 75.2 wt. % of graphite, 4 wt. % of P-1, 1 wt. % of CMC and 1 wt. % of carbon black. Electrode CE2 was thus obtained.
  • the peeling tests were performed in order to evaluate the adhesion of the electrode composition coating onto the metal support.
  • the test was performed on the electrodes prepared as described above, following the procedure of ASTM D903, working at a speed of 300 mm/min at 25° C.
  • Coin cells (CR2032 type, 20 mm diameter) were prepared in a glove box under an Ar gas atmosphere by punching a small disk of the negative electrode prepared according to E1, E2, E3, and CE1, CE2 together a balanced NMC positive electrode disk, purchased from CUSTOMCELLS.
  • the electrolyte used in the preparation of the coin cells was a mixture of 1M LiPF6 solution in EC/DMC 1/1 v/v with 2% wt VC and 10% wt F1 EC, from Solvionic; polyethylene separators (commercially available from Tonen Chemical Corporation) were used as received.

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